Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
  • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
  • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
  • B01J31/2208—Oxygen, e.g. acetylacetonates
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
  • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
  • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
  • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
  • C07C2/08—Catalytic processes
  • C07C2/26—Catalytic processes with hydrides or organic compounds
  • C07C2/30—Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/20—Olefin oligomerisation or telomerisation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/84—Metals of the iron group
  • B01J2531/847—Nickel
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • C07C2531/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
  • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron

Definitions

• the present invention relates to a novel catalytic composition for use in oligomerization processes, in particular for monoolefin dimerization.
• It also relates to a process for oligomerization, in particular dimerization, of monoolefins, using such a catalytic composition.
• catalysts for dimerization or co-dimerization of monoolefins such as ethylene, propylene, butenes or pentenes
• monoolefins such as ethylene, propylene, butenes or pentenes
• examples of such catalysts which can be cited are the products of the interaction of ⁇ -allyl nickel phosphine halides with Lewis acids (French patent FR-B-1 410 430), the products of the interaction of nickel phosphine halides with Lewis acids (United States patent U.S. Pat. No. 3,485,881) and the products of the interaction of certain nickel carboxylates with hydrocarbylaluminium halides (U.S. Pat. No. 3,321,546).
• U.S. Pat. No. 4,283,305 teaches that an association of a divalent nickel compound, a hydrocarbyl-aluminium halide with formula AlR m X 3 ⁇ m where R is a hydrocarbyl radical containing 1 to 12 carbon atoms, X is a chlorine or bromine atom, and m is a number from 1 to 2, and a compound with a Bronsted acid nature, leads to a catalytic composition that is more active than previously, and also less sensitive to the trace impurities which are routinely found in industrial olefinic feeds.
• said improved catalytic composition comprises the product resulting from bringing the following three constituents into contact in any order:
• the divalent nickel compound can be any compound soluble in a proportion of more than 1 g per litre in a hydrocarbon medium, more particular in the reactants and the reaction medium.
• nickel carboxylates are used with general formula (R 1 COO) 2 Ni, where R 1 is a hydrocarbyl radical, for example alkyl, cycloalkyl, alkenyl, aryl, aralkyl or alkaryl, containing up to 20 carbon atoms, preferably a hydrocarbyl residue containing 5 to 20 carbon atoms.
• Radical R 1 can be substituted by one or more halogen atoms, hydroxyl groups, ketone, nitro, cyano or other groups that do not interfere with the reaction.
• the two radicals R 1 can also constitute an alkylene residue containing 6 to 18 carbon atoms.
• nickel compounds are the following divalent nickel salts: octoate, 2-ethylhexanoate, decanoate, stearate, oleate, salicylate and hydroxy-decanoate.
• nickel 2-ethylhexanoate is used.
• the Bronsted acid compound has formula HY, where Y is an organic anion, for example carboxylic, sulphonic or phenolic.
• acids with a pK a of a maximum of 3 at 20° C. are used, more particularly those which are soluble in the nickel compound or in its solution in a hydrocarbon or another suitable solvent.
• One preferred class of acids comprises the group formed by halogenocarboxylic compounds with formula R 2 COOH where R 2 is a halogenated alkyl radical, in particular those which contain at least one halogen atom alpha to the —COOH group, with a total or 2 to 10 carbon atoms.
• a halogenoacetic acid with formula CX p H 3 ⁇ p —COOH is used where X is fluorine, chlorine, bromine or iodine, and p is a whole number from 1 to 3.
• X is fluorine, chlorine, bromine or iodine
• p is a whole number from 1 to 3.
• trifluoroacetic, difluoroacetic, fluoroacetic, trichloroacetic, dichloroacetic and chloroacetic acids are not limiting and it is also possible to use arylsulphonic acids, alkylsulphonic acids, fluoroalkylsulphonic acids, picric acid and nitroacetic acid.
• trifluoroacetic acid is used.
• the three constituents of the catalytic formula can be mixed in any order. However, it is preferable to first mixture the nickel compound with the organic Bronsted acid then to introduce the aluminium compound.
• the mole ratio of the hydrocarbylaluminium dihalide to the nickel compound, expressed as the Al/Ni ratio, is 2/1 to 50/1, preferably 2/1 to 20/1.
• the mole ratio of the Bronsted acid to the nickel compound is 0.25/1 to 10/1, preferably 0.25/1 to 5/1.
• Pre-conditioning the catalytic composition consists of mixing the three constituents in a hydrocarbon solvent, for example in an alkane or in an aromatic hydrocarbon, or in a halogenated hydrocarbon or, as is preferred, in a mixture with a composition analogous to that of the mixtures obtained in the dimerization or oligomerization reaction itself
• a hydrocarbon solvent for example in an alkane or in an aromatic hydrocarbon, or in a halogenated hydrocarbon or, as is preferred, in a mixture with a composition analogous to that of the mixtures obtained in the dimerization or oligomerization reaction itself
• the pre-conditioning solvent can principally be constituted by isohexenes.
• the mixture is generally produced by stirring in an inert atmosphere, for example in nitrogen or argon, at a controlled temperature of 0° C. to 80° C., preferably 10° C. to 60° C., for a period of 1 minute to 5 hours, preferably 5 minutes to 1 hour.
• the solution obtained is then transferred into the oligomerization reactor under an inert atmosphere.
• the hydrocarbylaluminium dihalide in the catalytic composition of the invention, can be enriched with an aluminium trihalide, the mixture of the two compounds then having formula AlR n X 3 ⁇ n , where R and X are as defined above and n is a number from 0 to 1 (limits excluded).
• the hydrocarbylaluminium dihalide compounds enriched in aluminium trihalide are obtained by mixing a hydrocarbylaluminium dihalide with formula AlRX 2 where R is a hydrocarbyl radical containing 1 to 12 carbon atoms, such as alkyl, aryl, aralkyl, alkaryl or cycloalkyl and X is a chlorine atom or a bromine atom, with an aluminium trihalide AlX 3 .
• Non limiting examples of such compounds which can be cited are: dichloroethylaluminium enriched with aluminium trichloride, the mixture having formula AlEt 0.9 Cl 2.1 , for example; dichloroisobutylaluminium enriched with aluminium trichloride, the mixture having formula AliBu 0.9 Cl 2.1 , for example, and dibromoethylaluminium enriched with aluminium tribromide, the mixture having formula AlEt 0.9 Br 2.1 , for example.
• the three constituents of the catalytic formula can be mixed in any order. It is also preferable to first mix the nickel compound with the organic Bronsted acid, then to introduce the aluminium compound.
• it is the mole ratio between the hydrocarbyl-aluminium dihalide enriched with aluminium trihalide and the nickel compound, expressed as the Al/Ni ratio, which is 2/1 to 50/1, preferably 2/1 to 20/1.
• the mole ratio of the Bronsted acid to the nickel compound is still 0.25/1 to 10/1, preferably 0.25/1 to 5/1.
• the invention also relates to a process for oligomerization, in particular dimerization, of monoolefins in the presence of the catalytic system defined above.
• monoolefins that can be dimerized or oligomerized are ethylene, propylene, butenes, pentenes and hexenes, used pure or as a mixture, contained in cuts from refining or from chemistry. These olefins can also be co-oligomerized between themselves.
• the process can be carried out in a reactor with one or more reaction stages in series, the olefinic feed and/or the previously pre-conditioned catalytic composition being introduced continuously, either to the first stage, or to the first and to any other stage.
• the process is generally carried out at a temperature of ⁇ 20° C. to +80° C., under pressure conditions such that at least the major portion of the reactants are maintained in the liquid phase or in the condensed phase.
• the catalyst can be deactivated, for example by injecting ammonia and/or an aqueous sodium hydroxide solution and/or an aqueous sulphuric acid solution.
• the unconverted olefins and alkanes which may be present in the feed are then separated from the oligomers by distillation.
• the products obtained by the process of the invention can be used, for example, as constituents for automobile fuels and/or as feeds for a hydroformylation process for synthesising aldehydes and alcohols.
• the catalyst was prepared in situ in the autoclave where oligomerization took place, without pre-conditioning, and used dichloroethylaluminium as the aluminium compound.
• a solution of 0.043 g of nickel 2-ethylhexanoate containing 13% by weight of nickel in 40 ml of isohexene solvent was introduced into a 250 ml stainless steel autoclave provided with stirring and wherein the temperature could be regulated by circulating water in an external envelope, followed by 10 g of a mother liquor prepared from 0.11 g of trifluoroacetic acid made up to 100 g with isohexene solvent, introduced with stirring. Finally, a solution of 0.18 g of dichloroethylaluminium in 50 ml of isohexene solvent was injected. This corresponded to 1.41 mmole of aluminium and an Al/Ni mole ratio of 15/1.
• a further flask purged with argon was used to prepare a solution of 0.18 g of dichloroethylaluminium in 50 ml of isohexene solvent.
• the solution obtained was slowly added to the nickel solution prepared above using a transfer needle. This corresponded to 1.41 mmole of total aluminium and to a Al/Ni mole ratio of 15/1. This was all pre-conditioned at 30° C. for 30 minutes with stirring.
• the pre-conditioned catalytic solution was transferred under argon to an autoclave as described in Example 1. 10 g of isohexenes was then introduced into the autoclave to make up the solvent, followed by 10.8 g of liquid propylene using a pressure lock. The temperature was rapidly raised to 40° C. The reaction was followed by periodically removing samples for gas chromato-graphic analysis. After 15 minutes of reaction, the conversion of propylene into a mixture of dimers, trimers and tetramers analogous to that of Example 1 was 86%.
• the pre-conditioned catalytic solution was transferred under argon to an autoclave as described in Example 1. 10 g of isohexenes was then introduced into the autoclave to make up the solvent, then 10.8 g of liquid propylene using a pressure lock. The temperature was rapidly raised to 40° C. The reaction was followed by periodically removing samples for gas chromatographic analysis. After 15 minutes of reaction, the conversion of propylene into a mixture of dimers, trimers and tetramers analogous to that of Example 1 was 89%.

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• 1999
  • 1999-05-27 FR FR9906749A patent/FR2794038B1/fr not_active Expired - Lifetime
• 2000
  • 2000-05-24 AR ARP000102541A patent/AR024094A1/es active IP Right Grant
  • 2000-05-25 TW TW089110140A patent/TW562695B/zh not_active IP Right Cessation
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